CN1027679C - Gas Separation Membranes with Selective Adsorption Properties - Google Patents

Abstract

A gas separation membrane with selective adsorption function belongs to a mixed gas separation membrane material. The membrane material is prepared by mixing additives composed of an adsorbent, metal powder or a solid catalyst and the like with a high molecular compound, has excellent separation performance, and has a separation coefficient alpha of a porous membrane₂/CO，H₂/N₂) > 3.74, while the permeation rate is J (H)₂) At 10^-4～10^-3And even higher.

Description

The invention relates to a membrane with selective adsorption performance for the separation of mixed gases. The membrane material is prepared by blending or reacting an adsorbent with selective adsorption performance, metal or metal salts, a solid catalyst, etc., with a high molecular polymer.

Membrane separation technology is widely used in the separation of various mixed substances due to its advantages of high efficiency, simple process, and low investment. It has attractive application prospects. the key of.

Problems such as the separation and adjustment of mixed gases are widely encountered in the industry. With the development of industry, the rational utilization of industrial tail gas containing H ₂ , CO, CH ₄ and other components is increasingly urgently placed in front of people. In the past, these tail gases or waste gases were difficult to be used economically and rationally except for combustion, resulting in waste of resources and environmental pollution. In recent decades, the development of membrane separation technology, especially membrane materials, has provided a great opportunity for the utilization of industrial tail gases. Industrial possibility, for example: separation and recovery of H ₂ and NH ₃ from tail gas of ammonia synthesis containing N ₂ . However, in some fields, the application of separation membrane technology is still subject to some restrictions and difficulties. These limitations and difficulties mainly come from whether the economy is reasonable, that is, if the level of separation membrane technology does not reach the expected economic calculation value, the application of this technology in this field will be very difficult. Undoubtedly, improving the separation efficiency of membrane materials is an important way to solve this problem.

Generally, separation membrane materials are divided into two categories: homogeneous membranes and porous membranes. The permeation mechanism of the homogeneous membrane is the dissolution-diffusion theory, that is, the gas is first adsorbed on the surface of the membrane, then dissolved, and diffuses in the membrane from the high pressure side to the low pressure side, and finally desorbed. In this process, what determines the permeability is the degree of dissolution of different gas molecules to the membrane material, so this mechanism is called the dissolution-diffusion mechanism. For porous membranes, what determines the permeability is the gas flow in the microporous layer, that is, the Kundsen flow, which determines the permeation rate and separation coefficient. That is to say, when the system is in an ideal situation where the interaction between molecules or molecules and pore walls can be ignored, then the separation factor α(A/B) of the membrane for mixed gases will be equal to the square root of the reciprocal of the molecular weight ratio, that is α(A/B)= $\sqrt{m{}_B}$ / $\sqrt{m{}_A}$ . For H ₂ /CO, H ₂ /N ₂ mixture, the ideal separation factor α is equal to $\sqrt{\mathrm{14}}$ , about 3.74. Obviously, the above theoretical treatment of porous membranes may have a large distance from the actual behavior of the membranes. Therefore, there is no porous membrane whose separation coefficient reaches this theoretical value so far.

After long-term research, it is found that the permeability and selectivity of ordinary polymer membranes to a certain gas are always inversely proportional. That is, increasing the permeability will decrease the selectivity, and conversely, increasing the selectivity will decrease the permeability. There is no doubt that a gas separation membrane with practical application value must have high permeation rate and high selectivity at the same time. Generally, homogeneous membranes have high selectivity, while porous membranes have high permeation rate, but the same polymer It is difficult for a membrane to have both of these two points, that is to say, it is difficult for you to "make" a homogeneous membrane and a porous membrane into one membrane, although you can make it into a composite membrane. In order to improve the permeability and selectivity of traditional polymer membranes, two or more compounds are copolymerized; or blended; or prepared into a composite with an ultra-thin active layer. membrane. To open up the application field of membrane separation technology.

Kenji Haratani of Japan once published an article [Surface (Day) 23, (1) 28 (1985)], proposing the performance target value of the gas separation membrane used in C ₁ chemistry, that is, in the case of a porous organic membrane, the operating pressure is ^Above 50kg/cm 2 , the maximum operating temperature is 150°C, its separation performance (capacity ratio) H ₂ /CO is 2~3, and the transmission coefficient is above 10 ^-4 (cm ³ ·cm/cm ² ·cmHg·sec) , that is to say, if the performance of the separation membrane reaches the above-mentioned value under the above-mentioned conditions, it has the possibility of _C1 chemical industrial application. In addition, many other industrial sectors, such as: synthetic ammonia petroleum processing (reforming process, etc.) and recovery from natural gas. Concentration of large amounts of hydrogen, etc., have put forward corresponding requirements.

In 1987, the U.S. Patent (US4,636,314) disclosed a polymer and inorganic blend film made by adding metal heteropolyacid or its salt to the polymer. In 1987, the Japanese patent (JP62, 202, 801) also disclosed a patent in which a polymer film was filled with metal powder (such as palladium, platinum, nickel, etc.) that could absorb hydrogen. However, none of the above-mentioned patents has published basic data on the chemical and physical properties of the membrane, as well as permeability and selectivity.

In 1988, the U.S. patent (US4,740,219) disclosed a silicon-containing molecular sieve Silicalite with a special structure of hydrophobic groups added to cellulose acetate (Nature, Vol. ), as an adsorbent. The solution is cast into a single-phase membrane, the membrane is used for the separation of 02/N ₂ , CO ₂ /H ₂ , the membrane has a large separation factor, but the basic data of the membrane permeation velocity J value is not published in the patent, and the membrane chemical and physical properties. Because for non-porous membranes, the separation factor α value is much larger than that of porous membranes. Therefore, for the separation membrane, the α value and the J value are equally important.

The purpose of the present invention is to utilize the adsorption properties (physical adsorption, chemical adsorption, adsorption state, etc.) , to provide a gas separation membrane with selective adsorption properties. The "behavior" of this membrane may not be limited by the "classical" membrane separation principles and theories. This membrane is a porous membrane or a non-porous membrane. A single-phase mixture film composed of adsorbents, metals, catalysts, etc., and polymer compounds with the function of selectively adsorbing gases.

Another object of the present invention is to provide a method for preparing the above-mentioned gas separation membrane having selective adsorption properties.

The third object of the present invention is to use the above-mentioned prepared membranes in membrane separation devices with practical value, such as H ₂ /CO, H ₂ /N ₂ , H ₂ /CH ₄ , CO ₂ /CH ₄ , O ₂ /N ₂ separation.

The invention prepares the separation membrane material by adding the substance with selective adsorption function to the polymer compound. The workers of the present invention accidentally discovered that the membrane separation material prepared by adding substances with selective adsorption function to the polymer compound has "behaviors" that cannot be explained by the above-mentioned "classical" theory, especially the membrane (porous membrane) The value of separation factor α (A/B) has exceeded the limit value of this "classical" theory, and the value of separation factor α is not only related to the molecular weight of the separated substance, in other words, it is the permeability of gas molecules with the same molecular weight. When passing through the membrane of the present invention, there may be different velocities, not the same velocities as the "classical" theory says. This contribution of the present invention not only greatly improves the permeation rate and separation factor of the gas separation membrane material, but also opens up a way to prepare a polymer gas separation membrane with excellent performance and selective adsorption function.

The present invention utilizes electron microscopy, temperature-programmed adsorption-desorption technology, and in-situ infrared technology to investigate the "process" of gas passing through the membrane material of the present invention. It is proposed that the adsorbed state possessed by the membrane facilitates the transport mechanism as the gas passes through the membrane of the present invention.

As mentioned above, the principle of separating the mixed gas of the porous membrane without active additives is mainly based on the molecular weight diffusion mechanism of Northen. The separation factor α of the mixed gas is only related to the molecular weight of the gas molecules, that is, α(AB)= $\sqrt{m{}_B}$ / $\sqrt{m{}_A}$ . However, in our porous membrane added with some kind of adsorbent, it is found that the value of α has exceeded the limit value of Northon's theory. Therefore, it can be confirmed that its permeation mechanism is not only related to the Nossen diffusion flow, but also related to the state of adsorption, diffusion, desorption and adsorption state, which we try to explain in the following discussion.

The present invention utilizes the permselective properties and physical and chemical properties of membranes made of polymer compounds to different gases, such as: softening point, acid resistance, alkali resistance, solubility, viscosity, tensile, tear strength and film-forming properties etc., select metal powders, adsorbents, and solid catalysts that can form an adsorption state with the separated gas molecules, and have suitable adsorption bond strengths or that can undergo oxidation-reduction reactions. The above raw materials are blended, fused or integrated by chemical or physical methods to form a polymer gas separation membrane with selective adsorption performance.

The above-mentioned metal powder should be understood as the elements of subgroups I, II, III, IV, V, VI, VII and group VIII in the 4th, 5th, and 6th periods of the periodic table of elements, such as: Pt, Pd, Zn, Ag , Co, Ni, Nb, Fe, Cu, Cr, W, Mo and other powders or their salts. Adsorbents include various types of molecular sieves, such as: X-type molecular sieves, A-type molecular sieves, ZSM-type molecular sieves, carbon molecular sieves, etc., diatomaceous earth, silicon microspheres, alumina, and various supports for chromatographic analysis (various models glazed or unglazed supports, etc.). Catalysts refer to oxide catalysts or metal/support catalysts including the above metals for heterogeneous catalytic reactions. These catalyst supports are usually SiO ₂ , AL ₂ O ₃ , SiO ₂ -Al ₂ O ₃ , ZnO, MgO and various types of Molecular sieve, etc.

One, or two or more of the above-mentioned adsorbents, metal powders or their salts, or catalysts in a ratio of 2% to 90% (by weight) and one, or two or more of the following organic polymers in a ratio of 98 % to 10% (weight) by blending, melting or reaction to produce a polymer gas separation membrane with selective adsorption properties.

The above polymer compounds refer to silicone rubber, polyvinyl alcohol, cellulose acetate (di- and tri-acetate), polysulfone, ethyl cellulose, polyacrylic acid, polyimide, nitrocellulose, etc., or two A mixture of the above polymer compounds.

Dissolve the above-mentioned organic polymer in a solvent at a certain ratio and concentration, add (or not add) suitable metal powder or its salt, adsorbent and solid catalyst, under certain conditions (temperature, stirring speed, humidity) etc.) to mix, fuse or react to obtain a glue solution, which is cast into a film on a clean and flat board in air or in water, or formed into a film using general-purpose film-forming equipment. Then age in hot air or hot water for a suitable time.

The above-mentioned glue solution can also be coated on a support substrate to form a composite film.

The above-mentioned mixing, fusion or reaction conditions are usually: the temperature is 10-50°C, and the stirring speed and time are suitable for sufficient mixing and smooth progress of the reaction.

The above-mentioned film-forming conditions are, in air: temperature 5-40°C, relative temperature 30-90%, in water: temperature 0-50°C, time 0.1-5 minutes, aging conditions of the film, in water: temperature 50-90°C , time 1-8 hours, film drying conditions, in air: temperature 20-80°C, in vacuum: temperature 20-50°C, time 1-8 hours.

The purpose of the present invention can also be achieved in the following manner:

According to the above formula and process, the adsorbent is carbon molecular sieve, sodium X type (13X) molecular sieve, calcium A type molecular sieve or other types of molecular sieve, and the polymer compound is ethyl cellulose, cellulose acetate or polysulfone.

The metal powder is cobalt powder or copper powder, and the polymer compound is ethyl cellulose, cellulose acetate or polysulfone.

The adsorbent is activated carbon and CuCl, and the polymer compound is polysulfone or cellulose acetate.

The adsorbent is Pd/Al ₂ O ₃ catalyst and CuCl, and the polymer compound is polysulfone.

The adsorbent can also choose 13X (sodium X type) molecular sieve, and the polymer compound is polysulfone or cellulose acetate.

The adsorbent can also be 5A type (calcium A type) molecular sieve, and the polymer compound is cellulose acetate.

The adsorbent can also be a molecular sieve containing Na ₂ O, Al ₂ O ₃ or SiO ₂ and the like, and the polymer compound is cellulose acetate.

The solvent in the above-mentioned film-making process can be ketones, esters, alcohols, amides, pyridine, tetrahydrofuran, dimethyl sulfoxide, dioxane, etc., or a mixture of two or more of the above-mentioned solvents.

The above-mentioned support substrate refers to a material that can increase the tensile and tear strength of the film. The present invention includes polyimide, polysulfone, polypropylene, polyester, non-woven fabric, cellulose polymer, and the like.

The amount of metal powder, adsorbent, and solid catalyst added to the above polymer compound is preferably 10-40% by weight, and the ratio of metal powder, adsorbent, and solid catalyst can be adjusted arbitrarily.

The metal powder, adsorbent, solid catalyst and other additives added to the membrane should preferably have a diameter of 0.5-150 μm. Of course, if economic reasons and performance of the additive are not considered, fine particles are preferred. These powder particles have a surface area of 10 to 1500 m ² /g. The particle size and distribution of additives are directly related to the specific surface area. For example, the specific surface area of reduced iron powder with an average particle size of 6 microns can reach 5160m ² /g. If you choose ultrafine powder <0.5 micron, its specific surface may be larger. If the additive is porous, its average pore size is 1A to 100 μm. Under the premise of maintaining film-forming conditions and film strength, the amount of additives can be unlimited, but preferably 10-40% by weight. The method of adding can be directly added to the glue solution, or soaked in a solvent first and then added. The powder particles can be uniformly or asymmetrically distributed in the film after stirring. Powder particles can also be added during film formation to form an additive powder layer on the surface of the film.

From the existing technologies and theories, we know that the thickness of the separation membrane has a direct impact on the permeability of the membrane. Therefore, how to make the membrane very thin to obtain a greater permeability has become a special technology. . However, the membrane made by the formulation and process of the present invention can be made very thick without affecting the permeation rate of the membrane. The thickness range of the membrane prepared by the above formulation and method is 1×10 ^-3 to 0.5 cm, certainly we are not excluded here, use the formula and method of the present invention to make the film thinner, or thicker, just illustrate the adaptability and uniqueness of the present invention here.

In the above-mentioned film-making process, we can also choose better conditions.

In the air, the better film-forming conditions are: temperature 20-35°C, relative humidity 40-60%, and in water: temperature 0-35°C, time 0.5-4 minutes. Aging of the prepared membrane is very necessary for the stability of the membrane, but it should be suitable. Aging under the following conditions is a better choice: water temperature 60-90°C, time 1-3 hours. Drying conditions in vacuum: temperature 10-40°C, time 1-5 hours.

The film made by the above formula and method is porous or non-porous, and is a single-phase film with certain extension and tear strength.

The gas permeability of the above-mentioned membranes is carried out on the CS-135-241 air permeability instrument recommended by ASTM1434V (1975) in the United States. The measurement method adopts the improved constant pressure volume method, and the 3400 gas chromatograph produced by Varian Company is used to analyze CO and _O2 , N ₂ , H ₂ and other components.

The performance of the membrane is: when separating H ₂ /CO and H ₂ /N ₂ , its separation coefficient α can be as high as 3.0 or more, even exceeding 3.74 to 5.3, and the permeability J (H ₂ ) [cm ³ (STP)/cm ² ·sec·cmHg]>10 ^-4 to 10 ^-3 .

The gas separation membrane with selective adsorption performance of the present invention has been confirmed by temperature-programmed adsorption-desorption technology, in-situ infrared technology, transmission electron microscope, and automatic adsorption measuring instrument to selectively adsorb certain gases such as: O ₂ , N ₂ , H ₂ , CO, CO ₂ , CH ₄ and lower hydrocarbons and other gases, and form an adsorption state on the surface, and the stability of this adsorption state and the amount of adsorption directly affect the permeability of the membrane.

Since the film of the present invention adds "active particles" such as adsorbents, metal powders, and solid catalysts, the surface of the polymer film is uneven, and it has both catalytic active points and adsorption active points. Adsorption of different intensities occurs with gas molecules, and an adsorption state is formed, and this adsorption state is likely to play a role in promoting transport.

Accompanying drawing is the electron microscope (SEM) picture of the separation membrane of the present invention, polymer compound is polysulfone, and additive is solid catalyst, wherein Fig. 1 and Fig. 2 are the surface of membrane, Fig. 3 and Fig. 4 are the section of membrane (enlarge The multiples are 1000 times and 2000 times respectively). The photos show that there are more solid powder particles (white particles) on the surface and inside of the membrane. The cross-sectional photos show that some of the added catalysts are wrapped with polysulfone, and some are in the pores of the polysulfone porous layer. When different gases pass through the membrane, the gas will inevitably contact with solid catalysts, adsorbents or metal powders, and there will be competitive adsorption, diffusion, desorption, or the formation of an adsorption state, which forms the membrane of the present invention. Unique penetration mechanism.

The present invention uses the Carlo Erba 1822 type automatic adsorption measuring instrument produced in Italy to measure adsorbent-polymer membrane and catalyst-polymer membrane, and find that their specific surface area, pore size distribution and pore size are different. Moreover, the permeability properties of the membrane (separation factor and permeation rate) are directly related to these data.

To sum up, compared with the prior art, the present invention has outstanding substantive features and remarkable technical progress.

1. The formula of the membrane and the basic data of the membrane (such as specific surface area, pore size distribution and pore size) show that the membrane has a unique composition and structure.

2. The membrane has excellent permeability, which is manifested in that the membrane has both high selectivity (separation factor) and high permeation rate. When the membrane is used to separate mixed gases such as H ₂ /CO and H ₂ /N ₂ , J(H ₂ ) is in the range of 10 ^-4 to 10 ^-2 , and α can be as high as 3.0 or even more than 3.74 to 5.3.

3. Because active additives are embedded in the membrane, the membrane has high separation factor and permeation rate at the same time, making it possible to make a thick membrane. The membrane thickness of the present invention can reach about 5mm.

For better illustrating the present invention, the present invention is further described by following examples:

example 1

2g molecular sieves (containing Na ₂ O, Al ₂ O ₃ , SiO _{2 ,} etc.) with a particle size of less than 0.1mm are added to the polysulfone dimethylformamide solution, the mixture is heated and stirred to form a glue, and poured onto a horizontal glass plate At a temperature of 20°C and a relative temperature of 50% in the air, the volatile solvent is dried to form a film, which is a porous film.

The above-mentioned membrane is immersed in the polysulfone solution for a certain period of time, and after taking it out, it is still dried under the above-mentioned conditions to become a secondary molded membrane. It is determined that the surface area of the membrane is 78.49m ² /g, the pore volume is 0.064cm ³ /g, the pore volume is 0.064cm ³ /g, and the average pore radius is 16.6 , membrane permeation rate J(H ₂ )>10 ^-3 , separation coefficient α(H ₂ /CO)>3.7, _{α(H 2} /N ₂ )>3.0.

Example 2

Take 4ml of saturated CuCl dimethylformamide solution and 16g of 20% polysulfone/dimethylformamide solution, heat and stir properly to dissolve them completely, then add 2g of Pd/Al ₂ O ₃ catalyst (particle size less than 0.01mm ) to stir, let it stand for a while, and then form a film on a horizontal glass. The measured surface area is 24.75m ² /g, the pore volume is 0.107cm ³ /g, and the average pore radius is 86.6A. This film is used to separate H ₂ / For CO and H ₂ /N ₂ , the permeation rate J(H ₂ )>10 ^-3 , separation factor α>3.1.

Example 3

Get ethyl cellulose (ethoxyl content 45～47%) and dissolve in following solvent: ethanol, butanone, tetrahydrofuran, pyridine, butyl acetate, dioxane, its concentration is 1～15% (weight), in Form a film (at room temperature) on a horizontal flat plate or polyester film, and dry it in vacuum for five hours to obtain a non-porous film. The above-mentioned glue solution can also be coated on a support material to form a composite membrane, for example, non-woven fabric, porous polyacrylonitrile, or porous polysulfone membrane.

According to the above formula and method, add an appropriate amount of plasticizer (such as: triethyl phosphate, tributyl phosphite, butyl phthalate, diethyl phthalate, tributyl borate, Triethylene glycol, glyceryl triacetate, polyethylene glycol 400, etc.), can greatly increase the permeation rate of the membrane.

Example 4

Take 15g of pyridine solution of ethyl cellulose (ethoxy content 45-47%) with a concentration of 4-7% (weight), add 1g of cobalt powder (particle size less than 200 mesh), and form a film on a horizontal glass plate. The membrane is leached in water, and then vacuum-dried at 30-50°C for 5 hours. The permeation rate J(H ₂ )>10 ^-4 , J(CO)>10 ^-4 , α(H ₂ /CO)>3.5, α (H ₂ /N ₂ ) > 3.5.

Example 5

Add 1g of molecular sieves (containing Na ₂ O, Al ₂ O ₃ , SiO _{2 ,} etc.) with a particle size of less than 0.10mm to the dimethylformamide solution of cellulose acetate, heat and stir the mixture properly to form a glue, and let it sit properly. Set at room temperature to form a porous membrane. After testing, the permeation rate J (H ₂ ) > 10 ^-2 , J (CO) > 10 ^-3 , separation factor α (H ₂ /CO) > 3.2, α (H ₂ /N ₂ ) > 3.5.

Example 6

According to the formula and preparation method of Example 5, ethyl cellulose was used instead of cellulose acetate, and the permeation rate J(H ₂ )>10 ^-2 and α(H ₂ /N ₂ )>3.5 of the prepared porous membrane.

Example 7

Carbon molecular sieves, sodium X-type (13X) molecular sieves or other types of molecular sieves are used as adsorbents, and the particle size is less than 0.10mm, which is added to the pyridine solution of ethyl cellulose or the dimethylformamide solution of cellulose acetate and polysulfone Next, the mixture is heated, stirred, left standing, on a glass plate, on a metal film tool or on a polyester film, the solvent is volatilized under air at a temperature of 20-30 ° C, and dried in vacuum or at room temperature to prepare a porous film.

Replacing the above-mentioned types of molecular sieves with various types of solid catalysts, such as: metal/support, metal oxides, etc., can also be made into porous membranes with excellent performance.

Example 8

Add 9 grams of dimethylformamide to 1 gram of molecular sieve (containing silicon, particle size less than 0.1mm), stir for 3 hours, add cellulose acetate dimethylformamide solution, stir evenly, remove air bubbles, and pour it on a flat and clean level On a glass plate (temperature 27°C, air pressure 630mmHg), scrape to form a film for 2-3 minutes, immediately put it into water for 2-3 minutes, then put the film into 85°C hot water for 1 hour to age, take it out and absorb the film Dry and dry naturally under the condition that the film is flat. In this film, J(H ₂ )=4.40×10 ^-4 , J(N ₂ )=9.09 to 9.27×10 ^-5 , and α(H ₂ /N ₂ )=4.84 to 5.25.

Example 9

Add 1 gram of copper powder (pre-reduced with hydrogen) with a particle size of less than 0.05mm into the dimethylformamide solution of polysulfone or cellulose acetate, heat the mixture properly, stir it, and form a glue, and let it stand properly. Membrane formed at room temperature and aged in hot air or hot water to prepare a gas separation membrane. The tested permeation rate J(H ₂ ) is 5.2×10 ^-4 , α(H ₂ /CO)=3.8, α( _{H 2} /N ₂ ) = 3.6.

Example 10

Soak CuCl solution in activated carbon, then dry and activate to obtain CuCl-containing activated carbon, add 1 g of this activated carbon to the dimethylformamide solution of polysulfone or cellulose acetate, properly heat and stir to form Glue solution, remove air bubbles, form a film on a horizontal clean glass plate at room temperature, and dry naturally. The permeation rate of this membrane is: J(H ₂ )=2.32×10 ^-2 , J(N ₂ )=6.37×10 ^-3 , J(CO)=6.35×10 ^-3 , J(CO ₂ )=4.91× 10 ^-3 , the separation factor is: α(H ₂ /N ₂ )=3.64, α(H ₂ /CO)=3.65.

The unit of permeation rate mentioned in this article is: cm ³ (STP)/cm ² ·sec·cmHg.

The best implementation is example 1, example 8, example 9, example 10.

Claims (7)

1. A polymer gas separation membrane with selective adsorption properties, characterized in that it consists of 2%-90% (weight) of one or more of the following metal salts, adsorbents, solid catalysts, and 98 %-10% of the following polymer compounds are made by blending, melting or reaction; The above-mentioned metal salts include Co, Cu, Cr nitrates and chlorides; Above-mentioned solid catalyst refers to Fe-Cr-Zn, P-Mo-Bi oxide catalyst and Pt/Al ₂ O ₃ , Pd/Al ₂ O ₃ , Pd-Pt/Al ₂ O ₃ metal/carrier catalyst; The above-mentioned adsorbent is activated carbon soaked in the above-mentioned metal salt; The high molecular compound mentioned above is cellulose diacetate, polysulfone, ethyl cellulose. 2. The gas separation membrane according to claim 1, characterized in that the adsorbent is CuCl, the solid catalyst is Pd/Al ₂ O ₃ , Pt/Al ₂ O ₃ , and the polymer compound is polysulfone. 3. The gas separation membrane according to claim 1, characterized in that the metal salt is Cu(NO ₃ ) ₂ , the solid catalyst is Pt/Al ₂ O ₃ , and the polymer compound is cellulose diacetate. 4. The gas separation membrane according to claim 1, characterized in that the solid catalyst is Fe-Cr-Zn or P-Mo-Bi oxide catalyst, and the polymer compound is polysulfone. 5. The gas separation membrane according to claim 1, characterized in that the particles of the adsorbent and solid catalyst are 0.5-150 μm or finer, the surface area is 10-1500 m ² /g or larger, and the average pore diameter is 1A-100 μm. 6. The gas separation membrane according to claim 5, characterized in that the membrane thickness is 1×10 ^-3 -0.5 cm. 7. The gas separation membrane according to claim 5 or 6, characterized in that the membrane is a porous membrane or a non-porous membrane.

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